WO2007091690A1

WO2007091690A1 - Raw material brass alloy for casting of semi-molten alloy

Info

Publication number: WO2007091690A1
Application number: PCT/JP2007/052412
Authority: WO
Inventors: Keiichiro Oishi
Original assignee: Mitsubishi Shindoh Co., Ltd.; Mitsubishi Materials Corporation
Priority date: 2006-02-10
Filing date: 2007-02-09
Publication date: 2007-08-16
Also published as: CN101379205A; JP2007211310A; US20090294087A1; US20090016927A1; JP5116976B2

Abstract

Disclosed is a raw material brass alloy for casting of a semi-molten alloy. The brass alloy has the following chemical composition (by mass): 8-40% of Zn, 0.0005-0.04% of Zr and 0.01-0.25% of P and, if required, one or more elements selected from 2-5% of Si, 0.05-6% of Sn and 0.05-3.5% of Al and, if further required, one or more elements selected from 0.005-0.45% of Pb, 0.005-0.45% of Bi, 0.03-0.45% of Se and 0.01-0.45% of Te, with the remainder being Cu and unavoidable impurities.

Description

Specification

Raw material brass alloy for semi-fusion gold fabrication

Technical field

TECHNICAL FIELD [0001] The present invention relates to a raw brass alloy for producing semi-fused gold, which can produce a brass alloy cake with fine crystal grains by producing the semi-fused gold without stirring the molten metal. This application claims priority based on Japanese Patent Application No. 2006-034126 filed in Japan on February 10, 2006, the contents of which are incorporated herein by reference.

Background art

[0002] Brass used in industry contains Zn: 8 to 50 mass%, and is distinguished according to its use. As a typical example, a brass alloy containing Zn: 8 to 20% by mass with the balance being Cu and unavoidable impurities, and ∑11: a brass alloy containing 25 to 35% by mass with the balance being Cu and unavoidable impurities. ∑11: Contains 35-45% by mass, and the balance is classified into brass alloys made of Cu and inevitable impurities. ∑11: Brass alloy containing 8 to 20% by mass has the color closest to the golden color, and its strength is also used in the manufacture of decorative products. In addition, brass alloys containing ∑11: 25-35% by mass are representative of copper: 70% by mass, zinc: 30% by mass, known as 7-3 brass with a uniform oc solid solution structure. In addition, a typical brass alloy containing 35 to 45% by mass of Zn is composed of 60% by mass of copper and 40% by mass of zinc, as 6-4 brass having an α + β solid solution structure. These brass alloys are widely used in the manufacture of various machine parts. Furthermore, a special brass alloy with improved hot-water flow by adding Si, a special brass alloy with one or more Pb, Bi, Se, Te added to improve free-cutting properties, and strength, corrosion resistance, resistance Special brass alloys with single or multiple additions of Al, Fe, Mn, Ni, etc. to improve wear are also known.

[0003] Even if the molten brass alloy is melted and formed by a usual method, a dendrite structure is formed and a brass alloy product having fine crystal grains cannot be obtained. Therefore, various forging methods have been proposed for obtaining brass alloy products with fine crystal grains, and a semi-molten alloy forging method has been proposed as an example. This method is less than the liquidus temperature of the alloy and is An alloy held in a slurry state in which solid metal and liquid metal are mixed within a temperature range exceeding the temperature (this alloy in slurry state is called “semi-fused gold!”) Is mechanically In this method, the mixture is cooled and solidified while stirring by stirring or electromagnetic stirring, and the stirring is stopped when a predetermined solid phase ratio is reached. According to this method, the dendrite produced in the solid-liquid mixed slurry is divided by stirring, and the primary crystal solid in the solid-liquid mixed slurry becomes spherical, so that the fluidity can be maintained up to a high solid phase ratio. ing. Also, according to this method, it is said that brass alloy ceramics with fine crystal grains can be obtained.

(See Non-Patent Document 1).

Non-Patent Document 1: “Metal Handbook Revised 5th Edition” edited by the Japan Institute of Metals, Maruzen (issued April 20, 1992), P1041 ~ 1042

Disclosure of the invention

Problems to be solved by the invention

[0004] However, in order to carry out the semi-fused metal forging method in which the molten metal is agitated, it is necessary to agitate while controlling the molten metal temperature, which increases the size of the apparatus, and injects extra gas into the molten metal depending on the conditions. There was a fear. Furthermore, considering the wear of the mold, it is necessary to lower the molten metal temperature. However, the conventional brass alloy cannot completely prevent the formation of a dendrite structure even if it is stirred in a semi-molten state. In addition, the fluidity of the molten metal deteriorated remarkably, which could eventually lead to forging defects.

The present invention has been made in view of the above circumstances, and can be used to produce a brass alloy product with fine crystal grains by producing a semi-fused metal without a stirring means. An object is to provide a raw material brass alloy for gold making.

Means for solving the problem

[0005] Therefore, the present inventors have improved the fluidity of the half-melted brass alloy without applying a stirring means for breaking up the dendrites in the liquid phase and granulating them, so that the half-melted brass can be obtained at a low temperature. Research was conducted to produce a brass alloy product with no crystal defects and fine crystal grains even when the alloy was manufactured. As a result, the following (A) to (D) were discovered for the first time.

(8) 211: Brass alloy containing 8-40% by mass of Zr: 0.0005-0.04 wt%, P: 0.01-0.25 wt% As a raw material alloy. The half-melted brass alloy obtained by completely melting and then cooling or the half-melted brass alloy obtained by re-dissolution is excellent in fluidity. It has been found that an alloy can be produced and therefore it is not necessary to perform a stirring process in the semi-fused state as in the prior art.

(B) By mass%, Zr: 0.0005 to 0.04 wt%, P: 0.01 to 0.25 wt%, the brass alloy according to (A) described above, and further by mass%, Si: 2 ~ 5%, Sn: 0.05-6% by mass and A1: 0.05-5.3.5% by mass of brass alloy containing one or more of 5% by mass is used as a raw material alloy and completely dissolved Then, the half-melted brass alloy obtained by cooling or the half-melted brass alloy obtained by re-melting has excellent fluidity, and when this half-melted brass alloy is prepared, It was found that the product can be manufactured, and therefore it is not necessary to perform the stirring process in the semi-fused state as in the prior art.

(C) In addition to the brass alloy described in the above (A) or (B), Pb: 0.005-0.45%, Bi: 0.005-0.45%, Se: 0.03 It was found that a brass alloy having a component composition containing one or more of ˜0.45% and Te: 0.01˜0.45% has the same effect.

(D) The brass alloy described in (A) to (C) is semi-fused and has good fluidity because the brass alloy described in (A) to (C) is completely dissolved and then cooled and solidified. This is due to the fact that fine α primary crystals, not dendrites, are crystallized during the process, and the brass alloys described in (ii) to (C) above are remelted. Research results such as that the molten brass alloy is due to the coexistence of fine particulate α solid phase in the liquid phase.

This invention was made based on the results of strong research,

(1) the mass ^{_{0/0, Zn: 8~40%}} , Zr:. 0. 0005~0 04%, P:. Containing 0.01 to 0 25%, the remainder being Cu and inevitable impurities components This is a raw material brass alloy for producing semi-fused gold.

(2) the mass ^{_{0/0, Zn: 8~40%}} , Zr:. 0. 0005~0 04%, P:. 0. 01~0 containing 25% addition, Si: 2 to 5% sn: 0. 05 to 6 mass ^_0/0 and A1:. 0. 05~3 containing 5 mass ^_0/0 one or more of, have a component composition balance being Cu and inevitable impurities You This is a raw brass alloy for semi-fused gold fabrication.

(3) The raw material brass alloy for producing semi-fused gold according to the above (1) or (2) further comprises, in mass%, Pb: 0.005-0.45%, Bi: 0.005-0.45%, Se: 0.03-0.45% Te: may have a component composition containing one or more of 0.01 to 0.45%.

The invention's effect

[0007] When the raw brass alloy for producing the semi-fused gold alloy of the present invention is dissolved to produce a solid-liquid mixed slurry half-melted brass alloy, and this half-fused brass alloy is produced by a usual method, Fine granular α initial phase is crystallized in the liquid phase or a solid phase coexists, so that it can be fabricated without impairing the fluidity of the half-melted brass alloy without stirring using a stirrer. Further, the brass alloy product obtained by forging the obtained half-melted brass alloy has an excellent effect that the crystal grains are further refined and the mechanical strength is further improved.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] Hereinafter, the present invention will be described in detail.

The raw brass alloy for semi-fused gold fabrication of the present invention contains, in mass%, Zn: 8 to 40%, Zr: 0.000 5 to 0.04%, P: 0.01 to 0.25%, the remainder being Cu and inevitable impurities It has a component composition consisting of

Further, the raw brass alloy for semi-fused gold fabrication of the present invention contains, in mass%, Zn: 8 to 40%, Zr: 0.0005 to 0.04%, P: 0.01 to 0.25%, and Si : Contains 2 to 5%, Sn: 0.05 to 6% by mass, and A1: 0.05-3. 5% by mass or more, and has a component composition of residual force Cu and inevitable impurity.

Further, the brass alloy for producing semi-fused gold according to the present invention is, in mass%, Zn: 8 to 40%, Zr: 0.0005 to 0.04%, P: 0.01 to 0.25%, Si: 2 to 5% , Sn: 0.05 to 6 mass ^_0/0 and A1:. 0.05 to 3 containing 5 wt% of one or more of the further, Pb:. 0.005~0 45%, Bi: 0.005~0.45% Se: 0.03 to 0.45%, Te: 0.01 to 0.45% of one or two or more may be included.

[0009] The raw brass alloy for producing semi-fused gold according to the present invention is prepared by preparing and storing ingots whose components have been adjusted in advance. It is possible to produce a brass alloy product with fine crystal grains by forging the obtained half-melted brass alloy.

The reason why the component composition of the raw brass alloy for producing semi-fused gold according to the present invention is limited as described above will be described.

Zn:

Zn, when added to Cu, lowers the melting point and improves the fluidity of the molten alloy, and further improves the corrosion resistance of the porcelain and improves the mechanical strength, but its content is 8 If it is less than mass%, the fluidity of the molten metal will be lowered. On the other hand, if it exceeds 40%, it will become hard and brittle and the mechanical strength will be lowered. Therefore, Zn contained in the brass alloy material for producing semi-fused gold according to the present invention is determined to be 8 mass% or more and 40 mass% or less.

Zr:

By coexisting with P, Zr promotes the crystallization of the fine granular ex initial phase in the semi-fused gold state, and by re-dissolving it makes the α solid phase coexist in the liquid phase of the half-melted brass alloy, The brass alloy obtained by improving the fluidity of the half-melted brass alloy and forging it, and having the effect of refining the crystal grains of the porcelain. If the content is less than 0.0005% by mass, the brass alloy is forged. This is not preferable because it does not exert a sufficient effect on the refinement of the crystal grains of the porcelain. On the other hand, if the content exceeds 0.04% by mass, the crystal grains of the brass alloy porcelain are increased, which is not preferable. Therefore, Zr contained in the brass alloy raw material for semi-fused metal fabrication of the present invention is determined to be 0.0005 mass% or more and 0.04 mass% or less.

P:

P coexists with Zr to promote the crystallization of fine granular oc initial phase in the semi-fused gold state, and the OC solid phase in the liquid phase of the half-melted brass alloy obtained by re-dissolution. Co-existing, thereby improving the fluidity of the half-melted brass alloy and forging brass alloy. On the other hand, it is not preferable because it does not exert a sufficient effect on the refinement of the crystal grains of the product. On the other hand, if the content exceeds 0.25% by mass, the crystal grains of the product become large, which is not preferable. Therefore, it is included in the raw brass alloy for semi-fused gold fabrication of this invention. The P content is determined to be not less than 0.01% by mass and not more than 0.25% by mass.

Si ゝ Sn, A1:

Si, Sn, A1 can improve mechanical strength, corrosion resistance, machinability, wear resistance, and peritectic reaction by adding one or more of them together with Zr, P, Cu and Zn. It is added as necessary in order to widen the composition range given to the steel, exhibit a remarkable crystal grain refining effect, and further improve the fluidity of the half-melted brass alloy.

In this case, if the Si content is less than 2% by mass, the desired effect cannot be obtained. On the other hand, if the Si content exceeds 5% by mass, the thermal conductivity is lowered and the fluidity of the half-melted brass is increased. It is preferable because it starts to decrease.

In addition, Sn has the effect of improving the seawater property in the above-mentioned corrosion resistance. If its content is less than 0.05% by mass, the desired effect cannot be obtained. On the other hand, Sn exceeds 6% by mass. Then, since it becomes brittle and thermal conductivity is lowered, the fluidity of the half-melted brass is lowered, which is preferable.

In addition to the above effects, A1 has the effect of improving the fluidity of the molten metal, reducing the loss of Zr, and further improving the erosion corrosion resistance of the corrosion resistance. If the amount is less than 0.05% by mass, the desired effect cannot be obtained. On the other hand, if it exceeds 3.5% by mass, the thermal conductivity decreases and the fluidity of the half-melted brass decreases. It is preferable because it becomes! /.

Therefore, Si is 2 to 5 mass contained in the semi-fusible alloy铸造raw material for the brass alloy of the present invention ^_0/0, Sn is 0.05 to 6 mass ^_0/0, A1 is 0.05 to 3.5 mass ⁰ / _Set to ₀ respectively. Of these Si 有効 Sn and A1 components, Si is the most effective, and it is most preferable to always contain Si. Other ingredients:

The raw brass alloy for producing semi-fused gold according to the present invention may further contain one or more of _Pb , _Bi , _Se , Te, etc., if necessary. ί if included in the brass alloy or, in the mass ^{_{0/0, Pb:. 0.}} 005~0 45%, Bi:. 0. 005~0 45%, Se:. 0. 03~0 45%, Te : It is included in the range of 0.01 to 0.45%.

The material brass alloy for semi-fused gold fabrication of the present invention has the above component composition.

The semi-fused brass in the solid-liquid mixed slurry state by melting this raw material brass alloy for semi-fused gold fabrication When an alloy is prepared and this half-melted brass alloy is produced by a usual method, a fine granular α primary phase is crystallized in the liquid phase of the half-melted brass alloy or the α solid phase coexists. It is possible to forge without damaging the fluidity of the half-melted brass alloy without providing a step, and the brass alloy product obtained by forging the obtained half-melted brass alloy has finer crystal grains. As a result, the mechanical strength is further improved. Example 1

[0012] (Example 1)

Prepare normal electrolytic copper as a raw material, charge this electrolytic copper into an electric furnace, melt it in an Ar gas atmosphere, add Zn and P when the molten copper temperature reaches 1200 ° C, If necessary, add brass, molten Si, Sn, Al, Pb, Bi, Se, Te, etc., and finally add Zr. The material brass alloy for semi-fused gold fabrication of the examples of the present invention having the component composition shown in Tables 1 to 8 below (hereinafter referred to as the material brass alloy of the examples of the present invention) 1 to Ingots consisting of 1 to 8 and 105 and a comparative brass alloy raw material brass alloy (hereinafter referred to as comparative raw material brass alloy) were produced. Further, a commercially available copper: 70 mass ^_0/0, Zinc: of 30 mass ^_0/0 7 3 brass and copper: 60 wt%, zinc: 40 consists wt% 6-4 brass in an Ar gas atmosphere A molten brass alloy with a temperature of 1200 ° C was prepared, and the resulting brass alloy melt was forged and solidified to have a conventional brass alloy for raw material for semi-fused metal fabrication having the composition shown in Table 7 below. An ingot made of gold (hereinafter referred to as a conventional raw material brass alloy) 1 to 2 was produced.

[0013] A part of the ingot made of the raw material brass alloy 1 to 105 of the example of the present invention obtained in Example 1, the raw material brass alloy 1 to 8 of the comparative example, and the conventional raw material brass alloy 1 to 2 was cut. The ingot thus cut and cut is heated to a predetermined temperature in the range exceeding the solidus temperature and less than the liquidus temperature, thereby remelting to produce a molten metal alloy. A quench specimen was prepared by ultra-quenching the molten alloy. By observing the microstructure of this rapidly cooled specimen with an optical microscope, the shape of the OC solid phase coexisting with the liquid phase in the molten metal alloy is estimated, and the average particle size is obtained. Shown in 8

[0014] It should be noted that a measurement of the average particle size of the solid phase was performed by etching the cut surface of the quenched specimen with nitric acid. Later observed and measured with an optical microscope:

[table 1]

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[] ^ []

[S002

[] 0021

[] 0022

From the results shown in Table 18, the raw material brass alloy 1 105 according to the example of the present invention shows that in the semi-molten state, the α solid phase of the quenching specimen exhibits fine particles. It is presumed that a fine α-solid phase coexists with the liquid phase. On the other hand, in the conventional raw material brass alloys 1-2, since the oc solid phase of the rapid cooling test piece is dendritic, the conventional raw material brass alloys 1-2 do not generate dendrites in the semi-molten state. It is estimated that Therefore, the half-melted brass alloy produced with the raw material brass alloy 1 to 105 of the embodiment of the present invention has excellent fluidity compared to the conventional half-melted brass alloy produced with the raw material brass alloy 1-2. The half-melted brass alloy obtained by melting the raw material brass alloys 1 to 105 in the examples of the present invention has a fine granular OC solid phase formed in the liquid phase, so that the half-melted brass alloy is not stirred. It can be seen that a forged product having fine crystal grains can be obtained even by forging. The comparative raw material brass alloys 1 to 6 containing Zn, Zr, and soot are out of the conditions of the present invention (range of the composition of the present invention). In the semi-molten state, dendrite is generated or crystal grains are refined. This is preferable because it becomes insufficient or brittle, and Zr: 0.0005 to 0.04%, P: 0.01 to 0.25% force S is contained in the coexistence of the comparative example. Brass alloys 7-8 are not free of dendrites.

(Example 2)

A part of the ingot made of the raw material brass alloys 1 to 105 of the above-described example of the present invention prepared in Example 1 and the raw material brass alloys 1 to 8 of the comparative example and the conventional raw material brass alloys 1 to 2 were cut out, respectively. The cut ingot is completely melted to produce a completely molten brass alloy melt, which is then cooled and maintained at a predetermined temperature within the range above the solidus temperature and below the liquidus temperature. A molten alloy was prepared, and a quenched specimen was prepared by ultra-quenching the molten metal alloy. By observing the microstructure of this rapidly cooled specimen with an optical microscope, the α primary crystal shape crystallized in the melt of the half-melted brass alloy was estimated, and the average particle size was obtained. As a result, almost the same result as in Example 1 was obtained. Obtained.

Industrial applicability

When the raw brass alloy for producing the semi-fused gold alloy of this invention is dissolved to produce a solid-mixed slurry half-melted brass alloy, and this half-fused brass alloy is forged by the usual method, the liquid phase of the half-fused brass alloy In addition, since the fine α initial phase was crystallized or a solid phase coexisted, it was possible to forge without impairing the fluidity of the half-melted brass alloy without providing a stirring means. The brass alloy product obtained by forging a half-melted brass alloy has one crystal grain There is an excellent effect that the mechanical strength is further improved by miniaturization. Therefore, the present invention is extremely useful industrially.

Claims

The scope of the claims

[1] in a weight ^{_{0/0, Zn: 8 ~}} 40%, Zr: 0.0005~0.04%, P: contains from 0.01 to 0.25%, for the semi-fusible alloy铸造having a component composition balance being Cu and inevitable impurities Raw material brass alloy.

[2] Mass ^{_{0/0, Zn: 8~40%}} , Zr: 0.0005~0.04%, P: contains 0.01 to 0.25%, further, Si: 2~5%, Sn: 0.05~6 mass ⁰ / ₀ and A1: 0.05 to 3.5 mass ⁰ / contain one or two or more of the _0, semi-fusible alloy铸造raw material for the brass alloy having a component composition balance being Cu and inevitable impurities.

[3] In addition, the mass ^{_{0/0, Pb: 0.005~0.45%}} , Bi: 0.005~0.45%, Se: 0.03~0.

The raw brass alloy for producing semi-fused gold according to claim 1 or 2, which has a component composition containing 45% or one or more of Te: 0.01 to 0.45%.